TW201426051A - Method of manufacturing optical waveguide and optical waveguide obtained by using the method - Google Patents

Abstract

A method of manufacturing optical waveguide includes a step of forming a sensitive resin layer composed of a sensitive resin composition on a substrate, a step of exposing a desired pattern, and a step of developing by using an alkaline developer containing bivalent or more metal ions. Furthermore, a method of manufacturing optical waveguide includes a step of forming a sensitive resin layer composed of a sensitive resin composition on a substrate, a step of exposing a desired pattern, a step of developing by using an alkaline developer, and a step of cleaning by using a cleaning agent containing bivalent or more metal ions or acid aqueous solution. In this invention, a method of manufacturing an optical waveguide with penetrability and good reliability and an optical waveguide obtained by using the method are provided.

Description

Optical waveguide manufacturing method and optical waveguide obtained by the same tube

The invention relates to a method for manufacturing an optical waveguide and an optical waveguide In particular, the present invention relates to a method of manufacturing an optical waveguide having the following steps, and an optical waveguide obtained by the manufacturing method: a step of forming a photosensitive resin layer on a substrate, and exposing a desired pattern The step and the step of performing development using an alkaline developer.

In recent years, in high-speed, high-density signal transmission between electronic components or between wiring boards, in the transmission of the previous electric wiring, mutual interference or attenuation of signals has become an obstacle, and high-speed and high-density have begun to be limited. In order to overcome this problem, those skilled in the art are investigating a technique of using light to connect between electronic components or between wiring substrates, that is, a so-called light interconnection. As a light transmission channel, a polymer optical waveguide has attracted attention in terms of ease of processing, low cost, high degree of wiring freedom, and high density.

As a form of a polymer optical waveguide, those skilled in the art consider the following The type is suitable: a type that is conceived to be applied to an opto-electric hybrid substrate on a glass epoxy substrate; or a flexible type that does not have a hard support substrate that connects the boards to each other.

One of the methods for forming a light guide tube easily and with high precision is well known. A method of forming a core pattern by exposure and development. In the above, the exposure process is a step of causing the photosensitive resin in the light-irradiating portion to be three-dimensionally crosslinked and insolubilized, and the developing process is a step of dissolving and removing the unreacted portion of the photosensitive resin in the undeveloped portion in the developing solution.

Previously, it has been known to use an organic solvent as a developing solution (example) For example, a method of performing development using an alkaline developer is also proposed from the viewpoint of the safety of the development process and the environmental load (for example, refer to the Japanese Patent Special Publication No. JP-A-63-81301). Japanese Patent Publication No. 6-258537 and Japanese Patent Laid-Open No. 2003-195079.

In order to make the material for forming an optical waveguide capable of applying an alkali developing process soluble In the alkaline developing solution, a functional group which exhibits acidity such as a carboxyl group or a phenol hydroxyl group is introduced into the material for forming the optical waveguide. Therefore, in the core pattern which is insolubilized by exposure, the acidic functional group is also neutralized by the alkaline developing solution to form a salt. In particular, when an alkaline developer containing an alkali metal compound such as sodium carbonate, potassium carbonate, sodium hydroxide or potassium hydroxide or an organic base such as tetramethyl ammonium hydroxide (TMAH) is used, The tendency of the resulting monovalent salt to be chemically unstable.

The core pattern with unstable salts remains as the inside of the core pattern becomes uneven Therefore, it is not preferable from the viewpoint of high transparency (low propagation loss), and is not preferable from the viewpoint of reliability of the optical waveguide.

The present invention has been made to solve the above problems, and its purpose is to provide A method for producing an optical waveguide having excellent transparency and reliability, and an optical waveguide manufactured by the method.

The present inventors have repeatedly conducted intensive studies and found that by the following The method can solve the above problems: a divalent or bivalent or higher metal ion is contained in the developing step, and/or a divalent or higher metal ion is contained in the cleaning step after development, or after development using an alkaline developing solution The optical waveguide is formed by a step of washing with an acidic aqueous solution.

In other words, the present invention provides a method for producing an optical waveguide comprising the steps of forming a photosensitive resin layer composed of a photosensitive resin composition on a substrate, and exposing the desired pattern. And a step of performing development using an alkaline developer containing divalent or higher metal ions; and (2) a method for producing an optical waveguide having a composition comprising a photosensitive resin composition on a substrate a step of exposing the photosensitive resin layer, a step of exposing the desired pattern, a step of developing using an alkaline developing solution, and a step of washing with a cleaning liquid or an acidic aqueous solution containing a metal ion of a divalent or higher valence or more (3) The method for producing an optical waveguide according to the above (2), wherein the alkaline developing solution in the developing step contains a divalent or a divalent or higher metal ion.

According to the production method of the present invention, the unstable monovalent salt remaining in the core pattern can be efficiently converted into a stable divalent or higher valence salt or effectively reduced. As a result of the acidic functional group, an optical waveguide excellent in transparency and reliability can be obtained with high productivity.

The above and other objects, features and advantages of the present invention will become more <RTIgt;

Fig. 1 is a graph showing a temperature profile in a reflow furnace in a reflow test carried out in the present invention.

Hereinafter, a method of manufacturing an optical waveguide of the present invention and an optical waveguide will be described in detail.

The method for producing an optical waveguide according to the present invention includes at least a step of forming a photosensitive resin layer composed of a photosensitive resin composition on a substrate, a step of exposing a desired pattern, and performing an alkali developing solution. The step of developing, and having a washing step as needed.

The method for producing an optical waveguide according to the present invention is characterized in that at least one of the developing step and the cleaning step after development contains divalent or divalent or higher metal ions, or is washed with an acidic aqueous solution after alkali development.

The preferred embodiment specifically has the following four aspects. That is, (a) a method of producing an optical waveguide comprising the steps of forming a photosensitive resin layer for forming an optical waveguide on a substrate, and exposing a desired pattern after forming a photosensitive resin layer, and exposing Subsequent use of alkaline development containing divalent or higher metal ions a step of developing a liquid; (b) a method of producing an optical waveguide having a step of forming a photosensitive resin layer for forming an optical waveguide on a substrate, and exposing a desired pattern after forming a photosensitive resin layer a step of performing development using an alkaline developing solution after exposure, and a step of cleaning using a cleaning liquid containing divalent or higher metal ions after development; (c) a method of manufacturing an optical waveguide tube, a step of forming a photosensitive resin layer for forming an optical waveguide on a substrate, a step of exposing a desired pattern after forming a photosensitive resin layer, and using an alkali having a divalent or higher metal ion after exposure. a step of developing the developer, and a step of cleaning using a cleaning solution containing a metal ion of a divalent or higher valence or more after development; and (d) a method of producing an optical waveguide having a light guide formed on the substrate a step of forming a photosensitive resin layer for forming a wave tube, a step of exposing a desired pattern after forming a photosensitive resin layer, and performing an exposure using an alkaline developing solution Film, and a step after the development step to be cleaned using the acidic aqueous solution.

The substrate used in the present invention is not particularly limited, and examples thereof include a silicon substrate, a glass substrate, a glass epoxy substrate, a plastic substrate, a metal substrate, a substrate with a resin layer, and a substrate with a metal layer. , plastic film, plastic film with resin layer, plastic film with metal layer, etc.

The method of forming the photosensitive resin layer on the substrate is not particularly limited, and examples thereof include a spin coating method, a dip coating method, a spray coating method, and a bar coating method. Bar coating), roll coating, curtain coating, gravure coating, screen coating, ink jet coating, etc. A method of coating a photosensitive resin composition for forming an optical waveguide.

When the photosensitive resin composition for forming a light guide tube is a suitable organic solvent When a photosensitive resin varnish for forming a light-diffusing wave tube is diluted, a drying step may be provided after forming a resin layer as needed. Examples of the drying method include heat drying, drying under reduced pressure, and the like. In addition, the drying methods may be used in combination as needed.

Other methods of forming the photosensitive resin layer include: using a photosensitive tree A method of forming a photosensitive resin layer by a build-up method of a photosensitive resin film composed of a fat composition. Further, as described later, it is generally preferred to use a film as a photosensitive resin film obtained by applying a photosensitive resin composition onto a support film and laminating a protective film on the photosensitive resin composition. A film composed of layers.

From the viewpoint of providing a highly productive optical waveguide manufacturing process, The method of forming the photosensitive resin layer is preferably a method of producing the photosensitive resin film for forming an optical waveguide by a build-up method as described above.

Hereinafter, the lower portion is formed by using a photosensitive resin film for forming an optical waveguide. The method of manufacturing the optical waveguide of the clad layer, the core, and the upper cladding layer is described as an example, but the present invention is not limited by this example.

First, in the first step, the photosensitive resin for forming the lower cladding layer is formed. The film is laminated on a substrate as described above. The method of laminating in the first step is not particularly limited, and examples thereof include a method of laminating by heating with a roll laminator or a flat laminator while heating.

In addition, in the present invention, the so-called flat type laminating machine refers to the product A laminating machine in which a layer material is sandwiched between a pair of flat plates and pressurized to press the flat plate, for example, a vacuum pressurizing laminator can be preferably used. The heating temperature here is preferably from 20 ° C to 130 ° C, and the pressure of the pressure is preferably from 0.1 MPa to 1.0 MPa, and the conditions are not particularly limited. When a protective film is present on the photosensitive resin film for forming a lower cladding layer, the protective film is removed and then laminated.

In addition, it is also possible to use a vacuum pressure type laminator before laminating The photosensitive resin film for forming a lower cladding layer was temporarily attached to the substrate by a roll bonding machine. Among them, from the viewpoint of improving the adhesion and flatting, it is preferred to temporarily attach while crimping, and to use a laminating machine having a heat roll while crimping. Pressing is performed while heating.

The lamination temperature is preferably from 20 ° C to 130 ° C. If the lamination temperature is greater than or equal At 20 ° C, the adhesion between the photosensitive resin film for forming the lower cladding layer and the substrate is improved. When the lamination temperature is 130 ° C or less, the fluidity of the resin layer is not excessively large at the time of roll bonding, and it is necessary to obtain Film thickness. From the above point of view, the laminating temperature is more preferably from 40 ° C to 100 ° C. The pressure at the time of lamination is preferably 0.2 MPa to 0.9 MPa, and the lamination speed is preferably 0.1 m/min to 3 m/min, and these conditions are not particularly limited.

The photosensitive resin film for forming a lower cladding layer laminated on a substrate is performed. Photocuring removes the support film of the photosensitive resin film for forming a lower cladding layer to form a lower cladding layer.

The irradiation amount of the active rays when forming the lower cladding layer is preferably from 0.1 J/cm ² to 5 J/cm ² , and these conditions are not particularly limited. Further, in order to efficiently cure the active light rays through the substrate, a double-sided exposure machine capable of simultaneously irradiating the active light from both sides can be used. Further, the active light can be irradiated while being heated. Further, heat treatment at 50 ° C to 200 ° C may be performed as needed after the photocuring.

In the second step, in the same way as the first step, the lower cladding layer A photosensitive resin film for forming an upper core portion. It is preferable that the photosensitive resin film for core formation is a photosensitive resin composition which is designed to have a refractive index higher than that of the lower cladding layer and which is formed of a photosensitive resin which can form a core pattern by active light. Composition.

In the third step, the core (core pattern) is exposed. Exposing the core pattern The method of light is not particularly limited, and examples thereof include a method of irradiating active rays with an image by a negative mask pattern called an artwork; and direct drawing by laser, failing A method of directly irradiating active light onto an image, such as a photomask.

Examples of the light source of the active light include an ultrahigh pressure mercury lamp and high pressure mercury. A light source, a mercury vapor arc lamp, a metal halide lamp, a xenon lamp, a carbon arc lamp, or the like, which can efficiently emit ultraviolet light. In addition to this, a light source such as a photographic photographic flood lamp or a fluorescent lamp that can efficiently emit visible light can be cited.

The irradiation amount of the active light when the core pattern is exposed is preferably 0.01 J/cm ² to 10 J/cm ² . When the irradiation amount is 0.01 J/cm ^{2 or more} , the hardening reaction proceeds sufficiently, and the core pattern is not lost by the development step described later. If the irradiation amount is 10 J/cm ² or less, the core pattern does not become excessive due to the excessive exposure amount. It is thick and can form a fine core pattern, which is preferable. From the above viewpoints, the irradiation amount of the active light is more preferably 0.05 J/cm ² to 5 J/cm ² , particularly preferably 0.1 J/cm ² to 3 J/cm ² .

When the core pattern is exposed, it may be exposed through a support film of a photosensitive resin film for core formation, or may be exposed after removal of the support film.

Further, after the exposure, from the viewpoint of improving the resolution and adhesion of the core pattern, post-exposure heating may be performed as needed. The time from the irradiation of the ultraviolet ray to the heating after the exposure is preferably within 10 minutes. When the time from the irradiation of the ultraviolet ray to the heating after the exposure is within 10 minutes, the active material produced by the irradiation of the ultraviolet ray does not lose its activity. The temperature for heating after exposure is preferably from 40 ° C to 160 ° C, and the time is preferably from 30 seconds to 10 minutes.

In the fourth step, when the film is exposed through the support film of the photosensitive resin film for core formation, the support film is removed, and development is performed using an alkali developer. The development method is not particularly limited, and examples thereof include a spray method, a dipping method, a liquid coating method, a spinning method, a brushing method, and a scrapping method. Further, the development methods may be used in combination as needed.

The alkaline developing solution is not particularly limited, and examples thereof include an alkaline aqueous solution, an alkaline semi-aqueous developing solution containing an alkaline aqueous solution and one or more organic solvents, and the like.

The base of the alkaline aqueous solution is not particularly limited, and examples thereof include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkali metal carbonates such as lithium carbonate, sodium carbonate, and potassium carbonate; and lithium hydrogencarbonate. , alkali metal bicarbonate such as sodium bicarbonate or potassium hydrogencarbonate; alkali metal phosphate such as potassium phosphate or sodium phosphate; alkali metal pyrophosphate such as sodium pyrophosphate or potassium pyrophosphate; sodium tetraborate or sodium metasilicate Salt; ammonium salt such as ammonium carbonate or ammonium hydrogencarbonate; tetramethylammonium hydroxide, triethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1,3-propanediol, 1, An organic base such as 3-diaminopropanol-2-morpholine or the like.

The bases of the alkaline aqueous solutions may be used singly or in combination of two or more kinds.

Further, the pH of the alkaline aqueous solution used for development is preferably from 9 to 14, more preferably from 10 to 13. The temperature of the alkaline aqueous solution used for development can be adjusted in accordance with the developability of the photosensitive resin layer for forming an optical waveguide. Further, a surfactant, an antifoaming agent, or the like may be mixed in the alkaline aqueous solution.

The above alkaline semi-aqueous developing solution contains only an alkaline aqueous solution and one or More than one organic solvent is not particularly limited. The pH of the alkaline semi-aqueous developing solution is preferably as small as possible in a sufficiently developable range, and the pH is preferably from 8 to 13, more preferably from 9 to 12.

The organic solvent is not particularly limited, and examples thereof include methanol and ethanol. Alcohols such as isopropanol, butanol, ethylene glycol, propylene glycol, and diethylene glycol; ketones such as acetone, methyl ethyl ketone, and 4-hydroxy-4-methyl-2-pentanone; Polyol alkyl ethers such as monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, and the like.

These organic solvents may be used singly or in combination of two or two. on. Further, the concentration of the organic solvent is usually preferably from 2% by weight to 90% by weight, and the temperature of the alkaline semi-aqueous developing solution can be adjusted in accordance with the developability of the photosensitive resin layer for forming an optical waveguide.

Moreover, a small amount of interfacial activity can also be mixed in the alkaline semi-aqueous developing solution. Agent, defoamer, etc.

In the above (a) to (c) which are aspects of the present invention, the above alkaline It is necessary to contain a divalent or higher metal ion in the developing solution and the cleaning liquid which will be described later in detail.

The metal ion of the divalent or higher divalent or higher is not particularly limited, and for example, it may be listed. For example: magnesium ion, calcium ion, zinc ion, manganese (II) ion, cobalt (II) ion, iron (II) ion, copper (II) ion, iron (III) ion, aluminum ion and the like.

From the viewpoint of the stability of the salt to be formed, among these metal ions, a divalent metal ion is preferred, and a magnesium ion or a calcium ion is particularly preferred.

These metal ions may be used singly or in combination of two or more kinds.

There is no particular limitation on the method of containing metal ions in the above alkaline developing solution. Examples thereof include a method of mixing or dissolving the following substances in an alkaline developing solution, and the like: a metal sulfate such as magnesium sulfate, calcium sulfate, zinc sulfate, manganese sulfate, cobalt sulfate, iron sulfate, copper sulfate, or aluminum sulfate; Metal chloride salts such as magnesium chloride, calcium chloride, zinc chloride, manganese chloride, cobalt chloride, ferric chloride, copper chloride, aluminum chloride; magnesium carbonate, calcium carbonate, zinc carbonate, manganese carbonate, cobalt carbonate, Metal carbonates such as iron carbonate, copper carbonate, and aluminum carbonate; metal hydroxides such as magnesium hydroxide, calcium hydroxide, zinc hydroxide, manganese hydroxide, cobalt hydroxide, iron hydroxide, copper hydroxide, and aluminum hydroxide .

In addition, water which originally contains the above metal ions can also be used as a base. Sex developer. The water is not particularly limited, and examples thereof include tap water and well water.

a divalent or higher divalent metal ion contained in the above alkaline developing solution The amount is preferably from 1 wt-ppm to 50,000 wt-ppm. If the amount of metal ions is greater than or equal to 1 wt-ppm, the unstable monovalent salt remaining in the core pattern can be effectively converted into a stable divalent or higher salt or more, if the amount of metal ions is less than or equal to 50,000 wt-ppm. No excess metal ions remain in the core pattern. From the above viewpoints, the amount of the divalent or higher divalent metal ions contained in the above alkaline developing solution is more preferably from 10 wt-ppm to 10,000 wt-ppm, particularly preferably from 30 wt-ppm to 5000 wt-ppm.

The treatment after development is preferably carried out by using a cleaning liquid containing water and a metal ion of divalent or higher valence or more (the washing step is referred to as a fifth step). The metal ion of divalent or divalent or higher is not particularly limited, and a divalent or divalent or higher metal ion similar to the above may be used.

From the viewpoint of the stability of the salt to be formed, among these metal ions, a divalent metal ion is preferred, and a magnesium ion or a calcium ion is particularly preferred.

These metal ions may be used singly or in combination of two or more kinds.

The method of containing the metal ions in the water is not particularly limited, and examples thereof include the same as those in the case where the metal developer is contained in the alkaline developing solution, and the materials are mixed or dissolved in the alkaline developing solution.

Further, water which originally contains the above metal ions may be used as the cleaning liquid. The water is not particularly limited, and examples thereof include tap water and well water.

The amount of the metal ions contained in the above cleaning liquid is preferably from 1 wt-ppm to 50,000 wt-ppm. If the amount of the metal ions is 1 wt-ppm or more, the unstable monovalent salt remaining in the core pattern can be converted into a stable divalent or higher-valent salt, and if the amount of the metal ions is 50,000 wt-ppm or less, Excess metal ions do not remain in the core pattern. From the above viewpoints, the amount of the metal ions contained in the above cleaning liquid is more preferably from 10 wt-ppm to 10,000 wt-ppm, particularly preferably from 30 wt-ppm to 5000 wt-ppm.

Further, an organic solvent, a surfactant, an antifoaming agent, or the like may be mixed into the cleaning liquid.

Further, in the above (d) which is an aspect of the present invention, a step of washing with an acidic aqueous solution after the step of performing development using an alkaline developing solution is a necessary condition. The washing method is not particularly limited, and examples thereof include a spray method, a dipping method, a coating method, a spinning method, a brushing method, and a scraping method. In addition, the cleaning methods may be used in combination as needed.

The acid in the acidic aqueous solution is not particularly limited, and examples thereof include inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid; carboxylic acids such as formic acid, acetic acid, malonic acid, and succinic acid; and lactic acid, salicylic acid, malic acid, and tartaric acid. Citric acid Isobaric acid (hydroxy acid) and the like. These acids may be used singly or in combination of two or more. Among the acids, sulfuric acid is preferred from the viewpoints of high acidity, low volatility, and low oxidizing power.

The pH of the acidic aqueous solution used for washing is preferably greater than 0 and less than Equal to 5. If the pH is greater than 0, the acidity and corrosivity are not excessively strong. If the pH is 5 or less, the unstable monovalent salt remaining in the core pattern can be effectively converted into the original acidic functional group. From the above point of view, the pH of the acidic aqueous solution is more preferably 0.1 to 4, particularly preferably 0.3 to 3. The temperature of the acidic aqueous solution can be adjusted in conjunction with the pH. Further, an organic solvent, a surfactant, an antifoaming agent, or the like may be mixed in the acidic aqueous solution.

If necessary, use water or a cleaning solution containing water and the above organic solvent. Wash in one step as a post-cleaning treatment. The organic solvent may be used singly or in combination of two or more. The concentration of the organic solvent is usually preferably from 2% by weight to 90% by weight, and the temperature of the organic solvent can be adjusted in accordance with the developability of the photosensitive resin layer for forming an optical waveguide.

If necessary, the pattern may be further cured by heating at about 60 ° C to 250 ° C or exposure of about 0.1 mJ/cm ² to 1000 mJ/cm ² as a treatment after the cleaning.

In the sixth step, the same method as the first step and the second step is used. In the method, a photosensitive resin film for forming an upper cladding layer is laminated on the lower cladding layer and the core pattern. Here, the photosensitive resin film for forming an upper cladding layer is designed to have a refractive index lower than that of the photosensitive resin film for forming a core portion. Moreover, the thickness of the upper cladding layer is preferably greater than the height of the core pattern.

Then, the upper cladding layer is formed by the same method as the first step. Photocuring is performed with a photosensitive resin layer (film) to form an upper cladding layer.

The irradiation amount of the active light rays at the time of forming the upper cladding layer is preferably from 0.1 J/cm ² to 30 J/cm ² , and these conditions are not particularly limited.

Further, when the active light is transmitted through the substrate, in order to perform the curing efficiently, a double-sided exposure machine capable of simultaneously irradiating the active light from both sides can be used. Further, the active light can be irradiated while heating at 50 ° C to 200 ° C. Further, heat treatment at 50 ° C to 200 ° C may be carried out as needed to perform treatment after photocuring.

After the upper cladding layer is formed, the support film is removed as needed, so that an optical waveguide can be formed.

Next, the photosensitive resin composition used in the present invention will be described.

The photosensitive resin composition is preferably a resin composition containing a carboxyl group and a phenolic hydroxyl group from the viewpoint of performing development using an alkali developer after exposure to a desired pattern. a compound of at least one of the groups.

Among them, from the viewpoints of transparency, heat resistance, and storage stability, a preferred photosensitive resin composition is (A) a carboxyl group-containing alkali-soluble polymer, (B) a polymerizable compound, and (C) photopolymerization. A photosensitive resin composition for forming an optical waveguide of an initiator.

Hereinafter, the component (A) used in the present invention will be described.

The alkali-soluble polymer having a carboxyl group in the component (A) is not particularly limited, and examples thereof include the polymers represented by the following (1) to (6).

(1) A carboxyl group-containing alkali-soluble polymer obtained by copolymerizing a compound having a carboxyl group and an ethylenically unsaturated group in a molecule and a compound having an ethylenically unsaturated group other than the above.

(2) Compounds having a carboxyl group and an ethylenically unsaturated group in the molecule In the copolymer of the compound having an ethylenically unsaturated group other than the above, a carboxyl group-containing alkali-soluble polymer obtained by partially introducing an ethylenically unsaturated group to the branched chain.

(3) a compound having a carboxyl group and an ethylenically unsaturated group in the molecule, and a carboxyl group-containing product obtained by reacting a compound having an epoxy group and an ethylenically unsaturated group in a molecule with a copolymer of a compound having an ethylenically unsaturated group and reacting the polybasic acid anhydride with the generated hydroxyl group Alkali soluble polymer.

(4) a compound having a hydroxyl group and an ethylenically unsaturated group in the molecule, and A carboxyl group-containing alkali-soluble polymer obtained by reacting an acid anhydride having an ethylenically unsaturated group with a copolymer of a compound having an ethylenically unsaturated group other than the above.

(5) making polybasic acid anhydrides, and difunctional epoxy resins with dicarboxylic acids or difunctional A carboxyl group-containing alkali-soluble polymer obtained by reacting an addition polymer of a phenol compound.

(6) combining a polybasic acid anhydride with a difunctional oxetane A carboxyl group-containing alkali-soluble polymer obtained by reacting a hydroxyl group of a dicarboxylic acid or an addition polymer of a difunctional phenol compound.

From the viewpoints of transparency and solubility in an alkaline developer, these The carboxyl group-containing alkali-soluble polymer is preferably a carboxyl group-containing alkali-soluble polymer represented by the above (1) to (4). Further, these polymers are (meth)acrylic polymers having a (meth)acrylonitrile group. Here, the (meth)acryl fluorenyl group means an acryl fluorenyl group and/or a methacryl fluorenyl group, and the so-called (meth)acrylic type polymer means acrylic acid, acrylate, methacrylic acid, and methyl group. Acrylates and derivatives of these substances are used as monomers to polymerize these monomers. The (meth)acrylic polymer may be a homopolymer of the above monomers, or two or more of these may be used. A copolymer obtained by polymerization. Further, the (meth)acrylic polymer may be an ethylene-containing compound other than the (meth)acryl fluorenyl group contained in the above-mentioned monomer and, if necessary, in a range that does not impair the effects of the present invention. A copolymer of a monomer other than the above having a saturated group. Further, the (meth)acrylic polymer may be a mixture of a plurality of (meth)acrylic polymers.

(A) The weight average molecular weight of the carboxyl group-containing alkali-soluble polymer is preferably It is 1,000~3,000,000. When the weight average molecular weight is 1,000 or more, the molecular weight is large, so that the strength of the cured product when the resin composition is formed is sufficient, and when the weight average molecular weight is 3,000,000 or less, the solubility in the developer containing the alkaline aqueous solution is (B) The compatibility of the polymerizable compound is good.

From the above point of view, the weight average molecular weight of the component (A) is better. 3,000~2,000,000, especially good is 5,000~1,000,000.

In addition, the weight average molecular weight in the present invention is by gel permeation chromatography. The value obtained by gel-permeation chromatography (GPC) and converted by standard polystyrene.

(A) Component The carboxyl group-containing alkali-soluble polymer can be specified by the following means The acid value, that is, in the step of forming a pattern by development, can be developed by using the above alkaline developing solution. For example, when the above alkaline aqueous solution is used, the acid value is preferably from 20 mgKOH/g to 300 mgKOH/g.

If the acid value of the component (A) is 20 mgKOH/g or more, development is easy. When the acid value of the component (A) is 300 mgKOH/g or less, the developer resistance does not decrease. From the above viewpoints, the acid value is more preferably from 30 mgKOH/g to 250 mgKOH/g, particularly preferably from 40 mgKOH/g to 200 mgKOH/g.

In addition, the term "developing liquid resistance" means that the development is not removed. The portion of the pattern is not affected by the developer.

In addition, when using an alkaline aqueous solution and one or more organic solvents When the alkaline semi-aqueous developing solution of the agent is used, the acid value of the component (A) is preferably from 10 mgKOH/g to 260 mgKOH/g. When the acid value of the component (A) is 10 mgKOH/g or more, development is easy, and if the acid value of the component (A) is 260 mgKOH/g or less, the development liquid resistance (the portion which becomes a pattern by the development is not affected by the developer) The nature of erosion) will not decrease. From the above viewpoints, the acid value of the component (A) is more preferably from 20 mgKOH/g to 250 mgKOH/g, particularly preferably from 30 mgKOH/g to 200 mgKOH/g.

Formulation of (A) component relative to the total amount of (A) component and (B) component The amount is preferably from 10% by weight to 85% by weight. When the amount of the component (A) is 10% by weight or more, the strength and flexibility of the cured product of the photosensitive resin composition for forming an optical waveguide are sufficient. When the amount of the component (A) is 85 wt% or less, the amount of the component (A) is less than or equal to 85 wt%. When the component (A) is entangled by the component (B) during exposure, it is easily cured, and there is no problem that the developer resistance is insufficient. From the above viewpoints, the compounding amount of the component (A) is more preferably from 20% by weight to 80% by weight, particularly preferably from 25% by weight to 75% by weight.

Hereinafter, the component (B) used in the present invention will be described.

The polymerizable compound of the component (B) is not particularly limited, and for example, it is preferably Examples thereof include a compound having a polymerizable substituent such as an ethylenically unsaturated group, a compound having two or more epoxy groups in the molecule, and the like.

Specific examples thereof include (meth) acrylate and vinylidene fluoride (vinylidene). Halide, vinyl ether, vinyl ester, vinyl pyridine, vinyl decylamine, arylated ethylene, etc., from the viewpoint of transparency, among these, (meth) acrylate and arylated ethylene are preferred. . As the (meth) acrylate, any of a monofunctional (meth) acrylate, a difunctional (meth) acrylate or a polyfunctional (meth) acrylate can be used.

The monofunctional (meth) acrylate is not particularly limited, and for example, Methyl acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, (A) Base) butyl acrylate, tert-butyl (meth) acrylate, butoxyethyl (meth) acrylate, amyl (meth) acrylate, hexyl (meth) acrylate, (meth) acrylate 2-ethylhexyl ester, heptyl (meth)acrylate, octylheptyl (meth)acrylate, decyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, Dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, (meth)acrylic acid Hexadecyl ester, octadecyl (meth)acrylate, behenyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, An aliphatic (meth) acrylate such as 3-chloro-2-hydroxypropyl (meth)acrylate or 2-hydroxybutyl (meth)acrylate; cyclopentyl (meth) acrylate or (meth) acrylate ring Hexyl ester, dicyclopentyl (meth)acrylate, An alicyclic (meth) acrylate such as dicyclopentenyl (meth) acrylate or isobornyl (meth) acrylate; phenyl (meth) acrylate or decyl phenyl (meth) acrylate; Base) p-cumyl phenyl acrylate, o-phenyl phenyl (meth) acrylate, 1-naphthyl (meth) acrylate, 2-naphthyl (meth) acrylate, benzyl (meth) acrylate, ( 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-(o-phenylphenoxy)propyl (meth)acrylate, 2-hydroxy-3-(meth)acrylate Aromatic (meth) acrylate such as 1-naphthyloxy)propyl ester or 2-hydroxy-3-(2-naphthyloxy)propyl (meth)acrylate; 2-tetrahydrofurfuryl (meth)acrylate , heterocyclic (meth) acrylate such as N-(methyl) propylene methoxyethyl hexahydrophthalimide, 2-(methyl) propylene methoxyethyl-N-carbazole An ethoxylate of the compounds; a propoxide of the compounds; an ethoxylated propoxylate of the compounds; a caprolactone modification of the compounds, and the like.

From the viewpoint of transparency and heat resistance, among them, the above alicyclic ring is preferred. a (meth) acrylate, a heterocyclic (meth) acrylate, an ethoxylate of the compounds, a propoxide of the compounds, an ethoxylated propoxide of the compounds, and a Lactone modified body.

The difunctional (meth) acrylate is not particularly limited, and for example, it can be exemplified: Alcohol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol II (Meth) acrylate, propylene glycol di(meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene glycol bis ( Methyl) acrylate, 1,3-butanediol di(meth) acrylate, 2-methyl-1,3-propanediol di(meth) acrylate, 1,4-butanediol di(methyl) Acrylate, neopentyl glycol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate , 2-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(methyl) An aliphatic (meth) acrylate such as acrylate, glycerol di(meth) acrylate or tricyclodecane dimethanol (meth) acrylate; cyclohexane dimethanol (meth) acrylate, ethoxylated ring Hexane dimethanol (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, An alicyclic (meth) acrylate such as bisphenol A di(meth) acrylate or hydrogenated bisphenol F di(meth) acrylate; bisphenol A di(meth) acrylate, bisphenol F bis ( Aromatic (meth) acrylate such as methyl acrylate, bisphenol AF di(meth) acrylate or fluorene type di(meth) acrylate; di(meth) acrylate isocyanuric acid Heterocyclic (meth) acrylates such as esters; ethoxylates of such compounds; propoxylates of such compounds; ethoxylated propoxylates of such compounds; caprolactone modified bodies of these compounds; Aliphatic epoxy (meth) acrylate such as pentanediol epoxy (meth) acrylate; Alicyclic dimethanol type epoxy (meth) acrylate, hydrogenated bisphenol A type epoxy (meth) acrylate, hydrogenated bisphenol F type epoxy (meth) acrylate, etc. alicyclic epoxy (methyl) Acrylate; resorcinol type epoxy (meth) acrylate, bisphenol A type epoxy (meth) acrylate, bisphenol F type epoxy (meth) acrylate, bisphenol AF type epoxy ( An aromatic epoxy (meth) acrylate such as methyl acrylate or fluorene epoxy (meth) acrylate.

The difunctional (meth)acrylic acid from the viewpoint of transparency and heat resistance Preferred among the esters are the above alicyclic (meth) acrylate, the above aromatic (meth) acrylate, the above heterocyclic (meth) acrylate, ethoxylates of these compounds, and propionic oxidation of these compounds. The ethoxylated propoxylate of these compounds, the caprolactone modified body of these compounds, the above alicyclic epoxy (meth) acrylate, and the above aromatic epoxy (meth) acrylate.

Trifunctional or trifunctional polyfunctional (meth) acrylates are not special The limitation is, for example, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, di(trimethylolpropane)tetra(meth)acrylate, pentaerythritol tetra(methyl). Aliphatic (meth) acrylates such as acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and heterocyclic formulas such as tris (meth) acrylate Acetate; ethoxylates of the compounds; propoxylates of the compounds; ethoxylated propoxylates of the compounds; caprolactone modifiers of the compounds; phenol novolak-type epoxy (A) An aromatic epoxy (meth) acrylate such as an acrylate or a cresol novolac type epoxy (meth) acrylate.

From the standpoint of transparency and heat resistance, these trifunctional or trifunctional Preferred among the above polyfunctional (meth) acrylates are the above heterocyclic (meth) acrylates, ethoxylates of these compounds, propoxylates of these compounds, ethoxylated propoxylates of these compounds, and the like. Caprolactone modification of the compound, the above aromatic Epoxy (meth) acrylate.

The above monofunctional (meth) acrylate, difunctional (meth) acrylate, three The functional or trifunctional or higher polyfunctional (meth) acrylate may be used singly or in combination of two or more kinds. Further, a (meth) acrylate having a different number of functional groups may be used in combination. Further, it can be further used in combination with other polymerizable compounds.

Moreover, the viewpoint of compatibility with (A) carboxyl group-containing alkali-soluble polymer The polymerizable compound (B) other than the above (meth) acrylate may, for example, be a polymerizable compound containing a compound having two or more epoxy groups in the molecule.

Preferred (B) polymerizable compound other than the above (meth) acrylate For example, hydroquinone type epoxy resin, resorcinol type epoxy resin, catechol type epoxy resin, bisphenol A type epoxy resin, tetrabromo double Phenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, bisphenol AD type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, bismuth type epoxy resin, etc. Bifunctional phenol glycidyl ether epoxy resin; hydrogenated bisphenol A epoxy resin, hydrogenated bisphenol F epoxy resin, hydrogenated 2,2'-biphenol epoxy resin, hydrogenated 4,4'-biphenol Hydrogenated bifunctional phenol glycidyl ether epoxy resin such as epoxy resin; phenol novolak epoxy resin, cresol novolak epoxy resin, dicyclopentadiene-phenol epoxy resin, dicyclopentane a trifunctional or trifunctional or higher polyfunctional phenol glycidyl ether type epoxy resin such as an enelenol type epoxy resin or a tetraphenol ethane type epoxy resin; a polyethylene glycol type epoxy resin or a polypropylene glycol type ring Bifunctional aliphatic alcohol glycidyl ether type epoxy tree such as oxygen resin, neopentyl glycol type epoxy resin, and 1,6-hexanediol type epoxy resin Lipid; cyclohexanediol type epoxy resin, cyclohexane dimethanol type epoxy resin, tricyclodecane dimethanol type epoxy resin, etc. Glycidyl ether type epoxy resin; trifunctional or trifunctional or higher polyfunctional aliphatic alcohol glycidyl ether type epoxy such as trimethylolpropane type epoxy resin, sorbitol type epoxy resin, glycerin type epoxy resin a resin; a difunctional aromatic glycidyl ester such as diglycidyl phthalate; a difunctional alicyclic glycidyl ester such as tetrahydrophthalic acid diglycidyl ester or hexahydrophthalic acid diglycidyl ester; a difunctional aromatic glycidylamine such as N,N-diglycidylaniline or N,N-diglycidyltrifluoromethylaniline; N,N,N',N'-tetraglycidyl-4, 4-diaminodiphenylethane, 1,3-bis(N,N-glycidylaminomethyl)cyclohexane, N,N,O-triglycidyl-p-aminophenol, etc. Functional or trifunctional or higher polyfunctional aromatic glycidylamine; alicyclic die acetal, alicyclic diepoxy adipate, alicyclic diepoxy carboxylate, vinyl cyclohexene Bifunctional alicyclic epoxy resin such as dioxide; 1,2-epoxy-4-(2-oxiranyl)cyclohexane of 2,2-bis(hydroxymethyl)-1-butanol a trifunctional or trifunctional such as an alkane adduct a polyfunctional alicyclic epoxy resin; a trifunctional or trifunctional or higher polyfunctional heterocyclic epoxy resin such as triglycidyl isocyanurate; a difunctional or the like such as an organic polyoxyalkylene type epoxy resin; A trifunctional or trifunctional or higher polyfunctional ruthenium-containing epoxy resin or the like.

From the viewpoint of transparency and heat resistance, among these compounds, it is preferred The bifunctional phenol glycidyl ether type epoxy resin, the hydrogenated bifunctional phenol glycidyl ether type epoxy resin, the trifunctional or trifunctional or higher polyfunctional phenol glycidyl ether type epoxy resin, and the above bifunctional alicyclic ring type An alcohol glycidyl ether phenol glycidyl ether type epoxy resin, the above bifunctional aromatic glycidyl phenol glycidyl ether type epoxy resin, the above bifunctional alicyclic glycidyl phenol glycidyl ether type epoxy resin, and the above double A functional alicyclic epoxy resin, the above polyfunctional alicyclic epoxy resin, the above polyfunctional heterocyclic epoxy resin, and the above difunctional or polyfunctional fluorene-containing epoxy resin.

The above compounds may be used singly or in combination of two or two. Further, it can be further used in combination with other polymerizable compounds.

(B) component polymerizability with respect to the total amount of component (A) and component (B) The compounding amount of the compound is preferably from 15% by weight to 90% by weight. When the amount of the component (B) is 15% by weight or more, the alkali-soluble polymer having a carboxyl group in the component (A) is easily entangled and hardened, and there is no problem that the developer resistance is insufficient, and the amount of the component (B) is adjusted. When the amount is 90% by weight or less, the film strength and flexibility of the cured film are sufficient. From the above viewpoints, the compounding amount of the component (B) is more preferably from 20% by weight to 80% by weight, particularly preferably from 25% by weight to 75% by weight.

Hereinafter, the component (C) used in the present invention will be described.

The photopolymerization initiator of the component (C) used in the present invention is not particularly limited as long as it can be polymerized by irradiation with active light such as ultraviolet rays, for example, when a compound having an ethylenically unsaturated group is used as the component (B). In the case of a compound, a photoradical polymerization initiator or the like can be mentioned.

The photoradical polymerization initiator is not particularly limited, and examples thereof include 2,2-dimethoxy-1,2-diphenylethane-1-one (2,2-dimethoxy-1,2-diphenylethan). -1-on) benzoin ketal; 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2- Hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4[4-(2-hydroxy-2-methylpropenyl) Α-hydroxyketones such as benzyl]phenyl}-2-methylpropan-1-one; methyl phenylglyoxylate, ethyl phenylglyoxylate, 2-hydroxy-2-hydroxyethyl hydroxyacetate Glyoxylic ester such as ethyl, hydroxyphenylacetic acid 2-(2-oxo-2-phenylethenyloxyethoxy)ethyl ester; 2-benzyl-2-dimethyl Amino-1-(4-morpholin-4-ylphenyl)-butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-? Phenyl-4-ylphenyl)-butane Α-amino ketone such as 1-ketone or 1,2-methyl-1-[4-(methylthio)phenyl]-(4-morpholinyl)-2-yl-propan-1-one; ,2-octanedione, 1-[4-(phenylthio), 2-(O-benzylidenehydrazide)], ethyl ketone, 1-[9-ethyl-6-(2-methylbenzene Mercapto)-9H-carbazol-3-yl], 1-(O-acetamidine) and other oxime esters; bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide, double Phosphine oxidation of (2,6-dimethoxybenzylidene)-2,4,4-trimethylpentylphosphine oxide, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-bis(methoxyphenyl)imidazole dimer, 2 -(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methoxyl) 2,4,5-triarylimidazole dimer such as phenyl)-4,5-diphenylimidazole dimer; benzophenone, N,N'-tetramethyl-4,4'-diamine Dibenzophenone, N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, etc. Ketone compound; 2-ethyl hydrazine, phenanthrenequinone, 2-tert-butyl hydrazine, octamethyl hydrazine, 1,2-benzoquinone, 2,3-benzoquinone Bismuth, 2-phenylindole, 2,3-diphenylanthracene, 1-chloroindole, 2-methylindole, 1,4-naphthoquinone, 9,10-phenanthrenequinone, 2-methyl Anthraquinone compounds such as benzoin, 2,3-dimethylhydrazine, benzoin ether, benzoin ethyl ether, benzoin phenyl ether, etc.; benzoin, benzoin, ethyl benzoin and other benzoin compounds; a benzyl compound such as a dimethyl ketal; an acridine compound such as 9-phenyl acridine or 1,7-bis(9,9'-acridinylheptane); N-phenylglycine, coumarin Prime.

In addition, in the above 2,4,5-triarylimidazole dimer, two triarylimimes The substituents of the aryl group of the azole moiety may be the same to form a symmetrical compound, or may be different to form an asymmetric compound.

From the viewpoints of hardenability, transparency, and heat resistance, the above compounds Preferred among the above α-hydroxyketones, the above-mentioned glyoxylic acid esters, the above-mentioned oxime esters, and the above phosphine oxides.

The above photoradical polymerization initiators may be used singly or in combination of two or more kinds. In addition, it can also be used in combination with a suitable sensitizer.

In addition, when an epoxy resin is used as the (B) component polymerizable compound, a photocationic polymerization initiator or the like is used as the (C) component photopolymerization initiator.

The photocationic polymerization initiator may, for example, be an aryldiazonium salt such as paramethoxy benzene diazonium hexafluorophosphate; diphenyl iodonium hexafluorophosphate or a hexafluorophosphate; Diarylsulfonium salt such as diphenylsulfonium fluorophthalate; triphenylsulfonium hexafluorophosphate; triphenylsulfonium hexafluoroantimonate; diphenyl-4-thiophenoxyphenylphosphonium hexafluorophosphate; Triarylsulfonium salt such as diphenyl-4-thiophenoxyphenylphosphonium fluoroantimonate, diphenyl-4-thiophenoxyphenylphosphonium pentafluorohydroxyphthalate; triphenylsulfonium hexafluorophosphate , triaryl selenium salt such as triphenyl selenium tetrafluoroborate or triphenyl selenium hexafluoroantimonate; dimethyl benzoyl hydrazine methyl hexafluoroantimonate; diethyl benzoyl hydrazine methyl hexafluoroantimonate Dialkyl benzhydryl methyl sulfonium salt; dihydroxy-4-hydroxy sulfonium salt such as 4-hydroxyphenyl dimethyl hydrazine hexafluoroantimonate or 4-hydroxyphenyl benzyl methyl hydrazine hexafluoroantimonate a sulfonate such as α-hydroxymethylbenzoin sulfonate, N-hydroxy quinone sulfonate, α-sulfonoxy ketone or β-sulfonyloxy ketone.

From the viewpoints of hardenability, transparency, and heat resistance, preferred among the above compounds are the above-mentioned triarylsulfonium salts. In the present invention, the polymerization initiators may be used singly or in combination of two or more kinds. In addition, it can also be used in combination with a suitable sensitizer.

The compounding amount of the component (C) component polymerization initiator is preferably from 0.1 part by weight to 10 parts by weight per 100 parts by weight of the total of the component (A) and the component (B). When the amount of the component (C) is 0.1 part by weight or more, the curing is sufficient, and when the amount of the component (C) is 10 parts by weight or less, sufficient light transmittance can be obtained. On the above point of view The blending amount of the component (C) is more preferably from 0.3 part by weight to 7 parts by weight, particularly preferably from 0.5 part by weight to 5 parts by weight.

In addition, in addition to this, the light guide used in the present invention may also be used as needed. A so-called additive such as an antioxidant, an anti-yellowing agent, an ultraviolet absorber, a visible light absorber, a colorant, a plasticizer, a stabilizer, or a filler is added to the photosensitive resin composition for forming a wave tube.

Hereinafter, the photosensitive resin for forming an optical waveguide tube used in the present invention The composition is explained.

The optical waveguide tube used in the present invention can be formed using a suitable organic solvent The photosensitive resin composition is diluted with a photosensitive resin composition to prepare a photosensitive resin varnish for forming an optical waveguide. The organic solvent to be used herein is not particularly limited as long as it can dissolve the resin composition, and examples thereof include aromatics such as toluene, xylene, mesitylene, cumene, and p-isopropyltoluene. a hydrocarbon; a cyclic ether such as tetrahydrofuran or 1,4-dioxane; an alcohol such as methanol, ethanol, isopropanol, butanol, ethylene glycol or propylene glycol; acetone or methyl ethyl ketone; , methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone and other ketones; methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, γ- Ester such as butyrolactone; carbonate such as ethylene carbonate or propylene carbonate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol Ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether Polyol alkyl ether such as diethylene glycol diethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, Glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate polyhydric alcohol alkyl ether acetates; N,N-dimethylformamide, phthalamide such as N, N-dimethylacetamide or N-methylpyrrolidone.

These organic solvents may be used singly or in combination of two or more.

Further, the concentration of the solid component in the resin varnish is usually preferably from 20% by weight to 80% by weight.

When preparing a photosensitive resin varnish for forming an optical waveguide, it is preferred to carry out mixing by stirring. The stirring method is not particularly limited, and from the viewpoint of stirring efficiency, it is preferred to carry out stirring using a propeller. The rotation speed of the propeller during stirring is not particularly limited, and is preferably from 10 min ^-1 to 1,000 min ^-1 . If the rotation speed is 10 min ^{-1 or more} , the components (A) to (C) and the components in the organic solvent can be sufficiently mixed. If the rotation speed is less than or equal to 1,000 min ^-1 , less bubbles are trapped due to the rotation of the propeller. . From the above point of view, the rotation speed of the propeller is preferably 50 min ^-1 to 800 min ^-1 , particularly preferably 100 min ^-1 to 500 min ^-1 .

The stirring time is not particularly limited, and it is preferably from 1 hour to 24 hours. When the stirring time is 1 hour or more, the components (A) to (C) and the components in the organic solvent can be sufficiently mixed. When the stirring time is 24 hours or less, the varnish preparation time can be shortened, and productivity can be improved.

The photosensitive resin varnish for forming an optical waveguide is preferably filtered using a filter having a pore diameter of 50 μm or less. When the pore diameter is 50 μm or less, large foreign matter or the like can be removed, and shrinkage or the like does not occur when the varnish is applied, and scattering of light transmitted through the core portion can be suppressed. From the above viewpoints, it is more preferable to use a filter having a pore diameter of 30 μm or less for filtration, and it is particularly preferable to use a filter having a pore diameter of 10 μm or less for filtration.

The photosensitive resin varnish for forming the optical waveguide is preferably reduced Depressurize by pressing. The defoaming method is not particularly limited, and examples thereof include a vacuum pump, a bell jar, and a defoaming device with a vacuum device. The pressure at the time of pressure reduction is not particularly limited, and a pressure at which the organic solvent contained in the resin varnish does not boil is preferred.

In addition, the decompression defoaming time is not particularly limited, and it is preferably 3 minutes~ 60 minutes. If the decompression defoaming time is 3 minutes or more, the bubbles dissolved in the resin varnish can be removed. If the decompression defoaming time is 60 minutes or less, the organic solvent contained in the resin varnish does not volatilize.

Hereinafter, the photosensitive resin for forming an optical waveguide used in the present invention The film is explained.

The photosensitive resin film for forming an optical waveguide tube used in the present invention can be used The photoreceptor resin composition for forming an optical waveguide, and the photosensitive resin varnish for forming an optical waveguide containing the component (A) to (C) are coated on a suitable support film. , remove the solvent. In addition, the photosensitive resin composition for forming an optical waveguide can be directly applied onto a support film to produce a photosensitive resin film for forming an optical waveguide of the present invention.

The support film is not particularly limited, and for example, polyethylene terephthalate can be cited. Polyesters such as esters, polybutylene terephthalate, polyethylene naphthalate; polyolefins such as polyethylene and polypropylene; polycarbonate, polyamide, polyimine, polyamidimide , polyether phthalimide, polyether thioether, polyether oxime, polyether ketone, polyphenylene ether, polyphenylene sulfide, polyarylate, polyfluorene, liquid crystal polymer, and the like.

From the viewpoint of flexibility and toughness, among the above compounds, preferred Polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, Polypropylene, polycarbonate, polyamide, polyimine, polyamidimide, polyphenylene ether, polyphenylene sulfide, polyarylate, polyfluorene.

In addition, the transmittance of the active light for exposure is lowered and the core pattern is lowered. From the viewpoint of the roughness of the side wall, it is more preferable to use a highly transparent support film. Such a highly transparent support film is exemplified by Cosmoshine A1517 and Cosmoshine A4100 manufactured by Toyobo Co., Ltd.

In addition, from the viewpoint of improving the peeling property from the resin layer, it is possible to visually A film which has been subjected to mold release treatment by a polyoxo compound or a fluorine-containing compound is used.

The thickness of the support film can be appropriately changed depending on the target softness, and it is preferably 3 Mm~250μm. When the thickness of the support film is 3 μm or more, the film strength is sufficient, and if the thickness of the support film is 250 μm or less, sufficient flexibility can be obtained. From the above viewpoints, the thickness of the support film is more preferably 5 μm to 200 μm, particularly preferably 7 μm to 150 μm.

The thickness of the support film used for the photosensitive resin film for core formation It is preferably 5 μm to 50 μm. When the thickness of the support film is 5 μm or more, the strength of the support is sufficient. When the thickness of the support film is 50 μm or less, the gap between the photomask and the photosensitive resin composition layer for forming the core portion is formed when the core pattern is formed. (gap) is not large, and pattern formation is good. From the above viewpoints, the thickness of the support film used for the photosensitive resin film for forming a core portion is preferably from 10 μm to 40 μm, particularly preferably from 15 μm to 30 μm.

Coating a photosensitive resin varnish or light guide for forming an optical waveguide on a support film A photosensitive resin film produced by forming a photosensitive resin composition for a wave tube may have a three-layer structure composed of a support film, a resin layer, and a protective film by attaching a protective film to the resin layer as needed.

The protective film is not particularly limited, and from the viewpoint of flexibility and toughness, Preferred examples include polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; and polyolefins such as polyethylene and polypropylene.

In addition, from the viewpoint of improving the peeling property from the resin layer, it is possible to visually A film which has been subjected to mold release treatment by a polyoxo compound or a fluorine-containing compound is used. The thickness of the protective film can be appropriately changed depending on the target flexibility, and is preferably from 10 μm to 250 μm. When the thickness of the protective film is 10 μm or more, the film strength is sufficient, and if the thickness of the protective film is 250 μm or less, sufficient flexibility can be obtained. From the above viewpoints, the thickness of the protective film is more preferably 15 μm to 200 μm, particularly preferably 20 μm to 150 μm.

The resin for forming a photosensitive resin film for an optical waveguide tube used in the present invention The thickness of the layer is not particularly limited, and the thickness after drying is usually 5 μm to 500 μm. When the thickness after drying is 5 μm or more, the thickness is sufficient. Therefore, the strength of the cured product of the resin film or the resin film is sufficient. When the thickness after drying is 500 μm or less, the film can be sufficiently dried, so that the amount of residual solvent in the resin film is not large. It will increase and will not foam when the cured product of the resin film is heated.

A photosensitive resin film for forming an optical waveguide obtained in this manner, for example It can be easily stored by winding into a roll shape. Alternatively, the roll-shaped film may be cut into a suitable size and formed into a sheet shape for storage.

Hereinafter, an optical waveguide formed by the manufacturing method of the present invention is used. Description.

The optical waveguide formed by the manufacturing method of the present invention is preferably light. The propagation loss is less than or equal to 0.3 dB/cm. If the light propagation loss is 0.3 dB/cm or less, the loss of light is small, and the intensity of the transmission signal is sufficient. In view of the above, light transmission The broadcast loss is preferably less than or equal to 0.2 dB/cm.

The optical waveguide formed by the manufacturing method of the present invention is preferably The optical waveguide is subjected to a high-temperature and high-humidity test at a temperature of 85 ° C and a humidity of 85% for 1000 hours, and the light propagation loss of the optical waveguide is 0.3 dB/cm or less. If the light propagation loss is 0.3 dB/cm or less, the loss of light is small, and the intensity of the transmission signal is sufficient. In addition, the high-temperature and high-humidity placement test at a temperature of 85 ° C and a humidity of 85% refers to a high-temperature and high-humidity placement test carried out under the conditions based on the JPCA standard (JPCA-PE02-05-01S).

The optical waveguide formed by the manufacturing method of the present invention is preferably After performing 1000 temperature cycling tests on the optical waveguide between -55 ° C and 125 ° C, the optical propagation loss of the optical waveguide is 0.3 dB/cm or less. If the light propagation loss is 0.3 dB/cm or less, the loss of light is small, and the intensity of the transmission signal is sufficient. Further, the temperature cycle test between -55 ° C and 125 ° C refers to a temperature cycle test carried out under the conditions based on the JPCA standard (JPCA-PE02-05-01S).

The optical waveguide formed by the manufacturing method of the present invention is preferably After performing three reflow tests on the optical waveguide at a maximum temperature of 265 ° C, the optical propagation loss of the optical waveguide is less than or equal to 0.3 dB/cm. If the light propagation loss is 0.3 dB/cm or less, the loss of light is small, the intensity of the transmission signal is sufficient, and the reflow process can be used to package the parts, so that the application range is widened. In addition, the reflow test of the maximum temperature of 265 ° C refers to a lead-free reflow test conducted under the conditions of JEDEC standard (JEDEC JESD22A113E).

The optical waveguide formed by the manufacturing method of the present invention has heat resistance and Excellent transparency, so it can be used as an optical transmission channel for optical modules. For example, the optical module may be connected to an optical fiber at both ends of the optical waveguide. a light guide tube with an optical fiber; a light guide tube with a connector attached to a connector at both ends of the light guide tube; and an optoelectronic composite substrate formed by combining the optical waveguide with the printed circuit board; Optical waveguide module, photoelectric conversion module combined with optical/electrical conversion element capable of converting optical signal and electrical signal; wavelength multiplexing/demultiplexing device formed by combining optical waveguide and wavelength division filter Wait.

In addition, the printed circuit board compounded in the photoelectric composite substrate is not particularly limited. Any of flexible substrates such as a glass epoxy substrate and a flexible substrate such as a polyimide substrate can be used.

[Examples]

Hereinafter, the present invention will be more specifically illustrated by the examples, but the present invention is not limited by the examples.

Manufacturing example 1

[Production of carboxyl group-containing alkali-soluble (meth)acrylic polymer P-1]

In a flask equipped with a stirrer, a condenser, a gas introduction tube, a dropping funnel, and a thermometer, 97 parts by weight of propylene glycol monomethyl ether acetate and 24 parts by weight of methyl lactate were weighed and stirred while introducing nitrogen gas.

The liquid temperature was raised to 80 ° C, and 18 parts by weight of N-cyclohexylmethyleneimine, 43 parts by weight of dicyclopentanyl methacrylate, and 53 parts by weight of 2-hydroxyethyl methacrylate were used for 3 hours. 20 parts by weight of methacrylic acid, 1 part by weight of 2,2'-azobis(isobutyronitrile), 65 parts by weight of propylene glycol monomethyl ether acetate, and 16 parts by weight of methyl lactate were added dropwise to the flask, and then The mixture was stirred at 80 ° C for 3 hours, then continuously stirred at 120 ° C for 1 hour, and cooled to room temperature.

Next, 0.07 parts by weight of dibutyltin laurate and 0.2 parts by weight of p-methoxyphenol were added, and the mixture was stirred while introducing air. Increase the liquid temperature to 60 ° C, use A mixture of 31 parts by weight of 2-methylpropenyloxyethyl isocyanate and 47 parts by weight of propylene glycol monomethyl ether acetate was added dropwise thereto over 30 minutes, and stirring was continued at 60 ° C for 4 hours to obtain a (meth)acrylic polymer. (P-1 solution (solid content: 40% by weight)).

[Measurement of acid value]

The acid value of P-1 was measured and found to be 60 mgKOH/g. In addition, the acid value is the root It was calculated from the amount of 0.1 mol/L potassium hydroxide aqueous solution necessary for neutralizing the P-1 solution. At this time, the point at which the added phenolphthalein as an indicator was changed from colorless to pink was used as a neutralization point.

[Measurement of Weight Average Molecular Weight]

Use GPC (made by Tosoh Corporation, trade name) SD-8022/DP-8020/RI-8020) The weight average molecular weight of P-1 (standard polystyrene conversion) was measured and found to be 31,000. In addition, the column was a Gelpack GL-A150-S/Gelpack GL-A160-S manufactured by Hitachi Chemical Co., Ltd.

Manufacturing Example 2

[Production of carboxyl group-containing alkali-soluble (meth)acrylic polymer P-2]

With mixer, condenser, gas inlet tube, dropping funnel and temperature In the flask, 97 parts by weight of propylene glycol monomethyl ether acetate and 24 parts by weight of methyl lactate were weighed and stirred while introducing nitrogen gas.

Raise the liquid temperature to 80 ° C and use N-cyclohexyl-n-butenylene for 3 hours. 18 parts by weight of an amine, 43 parts by weight of benzyl methacrylate, 53 parts by weight of 2-hydroxyethyl methacrylate, 20 parts by weight of methacrylic acid, and 1 part by weight of 2,2'-azobis(isobutyronitrile). A mixture of 65 parts by weight of propylene glycol monomethyl ether acetate and 16 parts by weight of methyl lactate was added dropwise to the flask, followed by stirring at 80 ° C for 3 hours, followed by 120 ° C. Stirring was continued for 1 hour to obtain a (meth)acrylic polymer P-2 solution (solid content: 40% by weight).

The acid value and the weight average molecular weight of P-2 were measured in the same manner as in Production Example 1, and found to be 96 mgKOH/g and 29,000, respectively.

Manufacturing Example 3

[Production of carboxyl group-containing alkali-soluble (meth)acrylic polymer P-3]

In a flask equipped with a stirrer, a condenser, a gas introduction tube, a dropping funnel, and a thermometer, 150 parts by weight of the above P-2 solution (solid content: 40% by weight) (solid content: 60 parts by weight), and dibutyltin laurate were weighed. 0.04 parts by weight, 0.1 parts by weight of p-methoxyphenol, and 21 parts by weight of propylene glycol monomethyl ether acetate were stirred while introducing air.

The liquid temperature was raised to 60 ° C, and 14 parts by weight of 2-methylpropenyloxyethyl isocyanate was added dropwise to the flask over 30 minutes, and then stirring was continued at 60 ° C for 4 hours to obtain a (meth)acrylic polymer. P-3 solution (solid content: 40% by weight).

The acid value and the weight average molecular weight of P-3 were measured in the same manner as in Production Example 1, and as a result, they were 58 mgKOH/g and 30,000, respectively.

Manufacturing Example 4

[Production of carboxyl group-containing alkali-soluble (meth)acrylic polymer P-4]

In a flask equipped with a stirrer, a condenser, a gas introduction tube, a dropping funnel, and a thermometer, 60 parts by weight of propylene glycol monomethyl ether acetate and 60 parts by weight of methyl lactate were weighed and stirred while introducing nitrogen gas.

The liquid temperature was raised to 80 ° C, and 18 parts by weight of N-cyclohexylmethyleneimine, 61 parts by weight of benzyl methacrylate, 18 parts by weight of 2-hydroxyethyl methacrylate, and methyl group were used for 3 hours. 37 parts by weight of acrylic acid, 2,2'-azobis(isobutyronitrile) 1 weight A mixture of 40 parts by weight of propylene glycol monomethyl ether acetate and 40 parts by weight of methyl lactate was added dropwise to the flask, followed by stirring at 80 ° C for 3 hours, followed by stirring at 120 ° C for 1 hour, and cooling to room temperature. until.

Then, adding 28 parts by weight of glycidyl methacrylate, p-methoxy 0.2 parts by weight of phenol and 43 parts by weight of propylene glycol monomethyl ether acetate were stirred while introducing air. The liquid temperature was raised to 80 ° C, 0.7 parts by weight of triphenylphosphine was added, and the mixture was stirred at 80 ° C for 1 hour, followed by stirring at 100 ° C for 24 hours to obtain a (meth)acrylic polymer P-4. Solution (solid content: 40% by weight).

The acid value and the weight average of P-4 were measured in the same manner as in Production Example 1. The amount was as follows, and the results were 80 mgKOH/g and 31,000, respectively.

Manufacturing Example 5

[Production of carboxyl group-containing alkali-soluble (meth)acrylic polymer P-5]

With mixer, condenser, gas inlet tube, dropping funnel and temperature In the flask, 94 parts by weight of propylene glycol monomethyl ether acetate and 40 parts by weight of methyl lactate were weighed and stirred while introducing nitrogen gas.

Raise the liquid temperature to 80 ° C and use N-cyclohexyl-n-butenylene for 3 hours. 20 parts by weight of an amine, 76 parts by weight of 2-ethylhexyl methacrylate, 25 parts by weight of 2-hydroxyethyl methacrylate, 27 parts by weight of methacrylic acid, and 2,2-azobis(isobutyronitrile) 0.8 A mixture of parts by weight, 63 parts by weight of propylene glycol monomethyl ether acetate, and 27 parts by weight of methyl lactate was added dropwise to the flask, followed by stirring at 80 ° C for 3 hours, followed by stirring at 120 ° C for 1 hour, and cooling to room. Warm up.

Next, 21 parts by weight of glycidyl methacrylate and p-methoxy group were added. 0.3 parts by weight of phenol and 32 parts by weight of propylene glycol monomethyl ether acetate The gas is stirred while stirring. The liquid temperature was raised to 80 ° C, 0.7 parts by weight of triphenylphosphine was added, and the mixture was stirred at 80 ° C for 1 hour, and then continuously stirred at 100 ° C for 24 hours to obtain a (meth)acrylic polymer P-5 solution (solid content). 40% by weight).

The acid value and weight average of P-5 were measured in the same manner as in Production Example 1. The amount was 56 mg KOH/g and 47,000, respectively.

Example 1

[Preparation of photosensitive resin varnish COV-1 for core formation]

In the wide-mouth polyethylene bottle, weighed as (A) carboxyl-containing alkali-soluble (A) 150 parts by weight of the above-mentioned P-1 solution (solid content: 40% by weight) of the acrylic polymer (60 parts by weight of solid content), and ethoxylated bisphenol A diacrylate as (B) polymerizable compound (Xinzhongcun) Manufactured by Chemical Industry Co., Ltd., trade name: A-BPE-10) 20 parts by weight, p-isopropylphenylphenoxyethyl acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: A-CMP-1E) 20 weight And as a (C) polymerization initiator, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one (Ciba refined) Manufactured by the company, trade name Irgacure 2959) 1 part by weight, bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide (manufactured by Ciba Specialty Chemicals Co., Ltd., trade name Irgacure 819)1 The parts by weight were stirred for 6 hours under the conditions of a temperature of 25 ° C and a number of revolutions of 400 rpm using a stirrer to prepare a photosensitive resin varnish for core formation.

Then, a polytetrafluoroethylene filter having a pore size of 2 μm (manufactured by Advantec Toyo Co., Ltd., trade name: PF020) and a membrane filter having a pore diameter of 0.5 μm (manufactured by Advantec Toyo Co., Ltd., trade name J050A) were used. The pressure filtration was carried out under the conditions of a temperature of 25 ° C and a pressure of 0.4 MPa. Then, using a vacuum pump and a bell jar, the pressure-reducing defoaming was performed for 15 minutes under the conditions of a reduced pressure of 50 mmHg to obtain a photosensitive resin varnish COV-1 for core formation.

[Production of Photosensitive Resin Film COF-1 for Core Formation]

The core-forming resin varnish was applied to a polyethylene terephthalate film (manufactured by Toyobo Co., Ltd., trade name A1517) using a coater (Multi Coater TM-MC manufactured by Hirano Tecseed Co., Ltd.). , on a non-treated surface having a thickness of 16 μm , dried at 100 ° C for 20 minutes, and then attached as a protective film of a release polyethylene terephthalate film (manufactured by DuPont Teijin Film Co., Ltd., trade name A31, having a thickness of 25 μm ), a photosensitive resin film COF-1 for core formation was obtained. At this time, the thickness of the resin layer can be arbitrarily adjusted by adjusting the gap of the coater. In the present embodiment, the thickness of the resin layer is adjusted so that the film thickness after hardening reaches 50 μm .

[Preparation of photosensitive resin varnish CLV-1 for forming a coating layer]

In the wide-mouth polyethylene bottle, 150 parts by weight of the above P-1 solution (solid content: 40% by weight) as (A) carboxyl group-containing alkali-soluble (meth)acrylic polymer was weighed (solid content: 60 parts by weight) 20 parts by weight of ethoxylated isomeric cyanuric acid triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name A-9300) as a (B) polymerizable compound, ethoxycyclohexane dimethanol diacrylate 20 parts by weight (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: A-CHD-4E), and 1-[4-(2-hydroxyethoxy)phenyl]-2 as (C) polymerization initiator -Hydroxy-2-methyl-1-propan-1-one (manufactured by Ciba Specialty Chemicals Co., Ltd., trade name Irgacure 2959) 1 part by weight, bis(2,4,6-trimethylbenzylidene) 1 part by weight of phenylphosphine oxide (manufactured by Ciba Specialty Chemicals Co., Ltd., trade name Irgacure 819), and stirred for 6 hours at a temperature of 25 ° C and a rotation speed of 400 min ^-1 using a stirrer to prepare a coating layer. Photosensitive resin varnish.

Then, a polytetrafluoroethylene filter having a pore size of 2 μm (manufactured by Advantec Toyo Co., Ltd., trade name: PF020) and a membrane filter having a pore diameter of 0.5 μm (manufactured by Advantec Toyo Co., Ltd., trade name J050A) were used. The pressure filtration was carried out under the conditions of a temperature of 25 ° C and a pressure of 0.4 MPa. Then, using a vacuum pump and a bell jar, the pressure-reducing defoaming was performed for 15 minutes under the conditions of a reduced pressure of 50 mmHg to obtain a photosensitive resin varnish CLV-1 for forming a coating layer.

[Production of photosensitive resin film CLF-1 for forming a cladding layer]

The above-mentioned coating layer forming photosensitive resin varnish CLV-1 was coated on a polyethylene terephthalate film using a coater (manufactured by Hirano Tecseed Co., Ltd., trade name: Multi Coater TM-MC) (Toyo Textile Co., Ltd.) Coated by Co., Ltd., trade name A1517, thickness 16 μm ) on a non-treated surface, dried at 100 ° C for 20 minutes, and then attached as a protective film of a stripped polyethylene terephthalate film (DuPont Teijin) Manufactured by Membrane Co., Ltd., trade name: A31, thickness: 25 μm ), a photosensitive resin film CLF-1 for forming a coating layer was obtained.

In this case, the thickness of the resin layer can be arbitrarily adjusted by adjusting the gap of the coater. In the present embodiment, the thickness of the resin layer is adjusted so that the film of the photosensitive resin film for forming the lower cladding layer after hardening is formed. The film thickness of the photosensitive resin film for forming an upper cladding layer having a thickness of 30 μm was 80 μm .

[Production of optical waveguide]

Roller laminating machine (made by Hitachi Chemical Co., Ltd.) Manufactured under the condition of a pressure of 0.4 MPa, a temperature of 80 ° C, and a speed of 0.4 m/min, the photosensitive resin film CLF- for forming a lower cladding layer of the protective film (A31) was removed. 1 Laminated on the FR-4 substrate (manufactured by Hitachi Chemical Co., Ltd., trade name E-679FB). Then, use a vacuum pressurizing laminator (Manufactured by Nihon Seisakusho Co., Ltd., trade name MVLP-500/MVLP-600), pressure bonding was carried out under the conditions of a pressure of 0.5 MPa, a temperature of 80 ° C, and a pressurization time of 30 seconds.

Then, after irradiating ultraviolet rays (wavelength: 365 nm) of 2000 mJ/cm ² using an ultraviolet exposure machine (manufactured by Dainippon Screen Co., Ltd., trade name MAP-1200-L), the support film (A1517) was removed to form a lower cladding. Floor.

Then, the photosensitive resin film COF-1 for core formation from which the protective film (A31) was removed was laminated under the conditions of a pressure of 0.4 MPa, a temperature of 80 ° C, and a speed of 0.4 m/min. On the lower cladding layer. Then, pressure bonding was carried out under the conditions of a pressure of 0.5 MPa, a temperature of 80 ° C, and a press time of 30 seconds using a vacuum press type laminator.

Then, the core (core pattern) was exposed to light by irradiating ultraviolet rays (wavelength: 365 nm) of 200 mJ/cm ² through a negative-type mask having a width of 50 μm using the above-described ultraviolet exposure machine. After heating at 80 ° C for 5 minutes, heating was carried out, after which the support film (A1517) was removed, and development was carried out using a 1 wt% aqueous sodium carbonate solution. Then, it was washed with a 0.3 wt% aqueous sulfuric acid solution (pH = 1), then washed with pure water, and dried by heating at 100 ° C for 1 hour.

Next, using the vacuum pressure type laminator, the photosensitive layer for removing the protective layer (A31) was removed under the conditions of a pressure of 0.5 MPa, a temperature of 80 ° C, and a press time of 30 seconds. The resin film CLF-1 is laminated on the core pattern and the lower cladding layer.

After irradiating ultraviolet rays of 2000 mJ/cm ² (wavelength: 365 nm), the support film (A1517) was removed, and then heat treatment was performed at 130 ° C for 1 hour, thereby forming an upper cladding layer to obtain an optical waveguide with a glass epoxy substrate. tube. Thereafter, a light guide tube having a waveguide length of 10 cm was cut using a dicing saw (manufactured by Disco Co., Ltd., trade name DAD-341).

Example 2 to Example 8 and Comparative Example 1 to Comparative Example 4

Preparation of photosensitive resin for core formation according to the blending ratio shown in Table 1 Paint COV-2~COV-4. Further, photosensitive resin varnishes CLV-2 to CLV-4 for forming a cover layer were prepared according to the blending ratio shown in Table 2. The photosensitive resin films COF-2 to COF-4 for forming a core portion and the photosensitive resin films CLF-2 to CLF-4 for forming a cladding layer were produced in the same manner as in the first embodiment.

The photosensitive resin film for forming the optical waveguide is used, and the use of Table 3 is used. An optical waveguide tube was produced in the same manner as in Example 1 except that the alkaline developing solution was used as an alkaline developing solution. Table 3 shows a combination of a photosensitive resin film for forming a core portion and a photosensitive resin film for forming a cladding layer used in the production of an optical waveguide, and a method for producing an optical waveguide.

Further, in Comparative Example 1 to Comparative Example 4, acid cleaning after development was not performed. And make a light guide tube.

* 1: (meth)acrylic polymer solution prepared in Production Example 1

*2: (meth)acrylic polymer solution prepared in Production Example 2

*3: (meth)acrylic polymer solution prepared in Production Example 3

*4: (meth)acrylic polymer solution prepared in Production Example 4

* 5: ethoxylated bisphenol A diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)

* 6: ethoxylated bismuth diacrylate (manufactured by Osaka Gas Chemicals Co., Ltd.)

* 7: p-Phenylphenylphenoxyethyl acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)

* 8: 2-hydroxy-3-(o-phenylphenoxy)propyl acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)

* 9: 1-[4-(2-Hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one (manufactured by Ciba Specialty Chemicals Co., Ltd.)

* 10: bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide (manufactured by Ciba Specialty Chemicals Co., Ltd.)

* 1: (meth)acrylic polymer solution prepared in Production Example 1

*11: (meth)acrylic polymer solution prepared in Production Example 5

* 12: ethoxylated iso-cyanuric acid triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)

* 13: Hydrogenated bisphenol A type epoxy acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)

* 14: ethoxycyclohexane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)

* 15: ethoxylated isomeric cyanuric acid diacrylate (manufactured by Toagosei Co., Ltd.)

* 9: 1-[4-(2-Hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one (manufactured by Ciba Specialty Chemicals Co., Ltd.)

* 10: bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide (manufactured by Ciba Specialty Chemicals Co., Ltd.)

Example 9

Using the above-described core-forming photosensitive resin film COF-1 and the coating layer-forming resin film CLV-1, an optical waveguide was produced by the following method.

[Production of optical waveguide]

Using a roll laminator (manufactured by Hitachi Chemical Co., Ltd., trade name: HLM-1500), the protective film was removed under the conditions of a pressure of 0.4 MPa, a temperature of 80 ° C, and a speed of 0.4 m/min. A photosensitive resin film CLF-1 for forming a lower cladding layer of A31) is laminated on an FR-4 substrate (manufactured by Hitachi Chemical Co., Ltd., trade name E-679FB). Then, using a vacuum pressure type laminating machine (manufactured by Nago Seisakusho Co., Ltd., trade name MVLP-500/MVLP-600) under the conditions of a pressure of 0.5 MPa, a temperature of 80 ° C, and a pressurization time of 30 seconds. Perform crimping.

Then, after irradiating ultraviolet rays (wavelength: 365 nm) of 2000 mJ/cm ² using an ultraviolet exposure machine (manufactured by Dainippon Screen Co., Ltd., trade name MAP-1200-L), the support film (A1517) was removed to form a lower cladding. Floor.

Then, the photosensitive resin film COF-1 for core formation from which the protective film (A31) was removed was used under the conditions of a pressure of 0.4 MPa, a temperature of 80 ° C, and a speed of 0.4 m/min. Laminated on the lower cladding layer. Then, pressure bonding was carried out under the conditions of a pressure of 0.5 MPa, a temperature of 80 ° C, and a press time of 30 seconds using a vacuum press type laminator.

Then, the core (core pattern) was exposed to light by irradiating ultraviolet rays (wavelength: 365 nm) of 200 mJ/cm ² through a negative-type mask having a width of 50 μm using the above-described ultraviolet exposure machine. After heating at 80 ° C for 5 minutes, heating was carried out, after which the support film (A1517) was removed, and development was carried out using a 1 wt% aqueous sodium carbonate solution containing magnesium sulfate in an amount of 100 wt-ppm of magnesium ions. Subsequently, it was washed with water containing magnesium sulfate in an amount of 100 wt-ppm of magnesium ions, washed with pure water, and dried by heating at 100 ° C for 1 hour.

Next, using the vacuum pressure type laminator, the photosensitive layer for removing the protective layer (A31) was removed under the conditions of a pressure of 0.5 MPa, a temperature of 80 ° C, and a press time of 30 seconds. The resin film CLF-1 is laminated on the core pattern and the lower cladding layer. After irradiating ultraviolet rays of 2000 mJ/cm ² (wavelength: 365 nm), the support film (A1517) was removed, and then heat treatment was performed at 130 ° C for 1 hour, thereby forming an upper cladding layer to obtain an optical waveguide with a glass epoxy substrate. tube. Thereafter, a light guide tube having a waveguide length of 10 cm was cut using a cutter (manufactured by Disco Co., Ltd., trade name DAD-341).

Example 10 to Example 20 and Comparative Example 5 to Comparative Example 8

The photosensitive resin films COF-1 and COF-4 for forming a core portion, and the resin films CLV-1 and CLV-4 for forming a cladding layer were used, and the alkaline developing solution and the cleaning solution shown in Table 4 were used as the cleaning solution. An optical waveguide tube was produced in the same manner as in Example 9 except for the alkaline developing solution and the cleaning solution. Table 4 shows a combination of a photosensitive resin film for forming a core portion and a photosensitive resin film for forming a cladding layer used in the production of an optical waveguide, and a method for producing an optical waveguide.

[Determination of Light Propagation Loss]

A VCSEL (manufactured by EXFO Corporation, trade name FLS-300-01-VCL) having a wavelength of 850 nm as a center wavelength was used as a light source, and a light-receiving sensor (manufactured by Advantest Co., Ltd., trade name: Q82214), an incident fiber was used. (GI-50/GI-125 multimode fiber, NA=0.20) and exit fiber (SI-114/SI-125, NA=0.22), using the cutback method (measuring the length of the waveguide) The light propagation loss of the optical waveguide (guide tube length of 10 cm) obtained in Examples 1 to 20 and Comparative Examples 1 to 8 was measured for 10 cm, 5 cm, 3 cm, and 2 cm), and was measured on the following basis. Evaluation.

○: Less than or equal to 0.3 dB/cm

×: greater than 0.3 dB/cm

[High temperature and high humidity test]

Using Examples 1 to 20 and Comparative Examples using a high-temperature and high-humidity tester (manufactured by Espec Co., Ltd., trade name: PL-2KT) under the conditions of the JPCA standard (JPCA-PE02-05-01S) The light-guide tube (the length of the waveguide tube of 10 cm) obtained in 1 to Comparative Example 8 was subjected to a high-temperature and high-humidity test for 1000 hours at a temperature of 85 ° C and a humidity of 85%.

The light propagation loss of the optical waveguide after the high-temperature and high-humidity test was measured using the same light source, light-receiving element, incident optical fiber, and outgoing optical fiber as described above, and evaluated based on the following criteria.

○: Less than or equal to 0.3 dB/cm

×: greater than 0.3 dB/cm

[Temperature cycle test]

Using a temperature cycle tester (manufactured by Nanben Chemical Co., Ltd., trade name ETAC WINTECH NT1010), based on the JPCA standard (JPCA-PE02-05-01S), at a temperature between -55 ° C and 125 ° C The optical waveguides (the length of the waveguide of 10 cm) obtained in Examples 1 to 20 and Comparative Examples 1 to 8 were subjected to 1000 temperature cycle tests. Detailed temperature cycling test conditions are shown in Table 5.

The light propagation loss of the optical waveguide after the temperature cycle test was measured using the same light source, light receiving element, incident optical fiber, and outgoing optical fiber as described above, and evaluated based on the following criteria.

○: Less than or equal to 0.3 dB/cm

×: greater than 0.3 dB/cm

[Reflow test]

Using the reflow tester (manufactured by Furukawa Electric Co., Ltd., trade name Salamander XNA-645PC), the examples 1 to 20 and the comparative example 1 were carried out under the conditions of IPC/JEDEC J-STD-020B. ~ The optical waveguide obtained in Comparative Example 8 (the length of the waveguide is 10 cm) is the highest in three times. The reflow test at a temperature of 265 °C. The detailed reflow conditions are shown in Table 6, and the temperature profile in the reflow furnace is shown in Fig. 1.

The light propagation loss of the optical waveguide after the reflow test was measured using the same light source, light receiving element, incident optical fiber, and outgoing optical fiber as described above, and evaluated based on the following criteria.

○: Less than or equal to 0.3 dB/cm

×: greater than 0.3 dB/cm

The measurement results of the above light propagation loss are shown in Table 7.

According to Table 7, the optical waveguide formed by the manufacturing method of the present invention is known. The tube is excellent in transparency and reliability. On the other hand, it is understood that an optical waveguide formed by a method for producing an optical waveguide which is not in the scope of the present invention, that is, a photoconductive tube which is formed by treatment without using a divalent or higher metal ion at the time of development and/or development The waveguide or the optical waveguide formed without acid cleaning after development has poor transparency and reliability.

[Industrial availability]

By using the manufacturing method of the present invention, residual instability in the core pattern can be achieved The monovalent salt is effectively converted into a stable divalent or bivalent salt or the unstable monovalent salt remaining in the core pattern is effectively reduced to an acidic functional group, and as a result, transparency can be obtained with high productivity. Optical waveguides with excellent properties and reliability.

Although the present invention has been disclosed in the above preferred embodiments, the present invention is not intended to limit the invention, and it is possible to make a few changes without departing from the spirit and scope of the invention. And the scope of the present invention is defined by the scope of the appended claims.

Claims (18)

A method for producing an optical waveguide comprising: a step of forming a photosensitive resin layer composed of a photosensitive resin composition on a substrate; a step of exposing a desired pattern; and using a divalent or higher valence or higher a step of developing an alkali developing solution of a metal ion comprising (A) a carboxyl group-containing alkali-soluble polymer, (B) a polymerizable compound, and (C) a photopolymerization initiator Resin composition. The method for producing an optical waveguide according to claim 1, wherein the (A) carboxyl group-containing alkali-soluble polymer is a carboxyl group-containing alkali-soluble (meth)acrylic polymer. A method for producing an optical waveguide comprising: a step of forming a photosensitive resin layer composed of a photosensitive resin composition on a substrate; a step of exposing a desired pattern; and developing using an alkaline developing solution And a step of washing with a cleaning solution containing a divalent or higher metal ion or an acidic aqueous solution, wherein the photosensitive resin composition comprises (A) a carboxyl group-containing alkali-soluble polymer, and (B) polymerizability A resin composition of the compound and (C) a photopolymerization initiator. The method for producing an optical waveguide according to claim 3, wherein the (A) carboxyl group-containing alkali-soluble polymer is a carboxyl group-containing alkali-soluble (meth)acrylic polymer. The method for producing an optical waveguide according to claim 3, wherein the alkaline developing solution in the developing step contains a divalent or higher metal ion. The method for producing an optical waveguide according to any one of claims 1 to 5, wherein the divalent or higher metal ion is magnesium and/or calcium. The method for producing an optical waveguide according to claim 3, wherein the acidic aqueous solution is an aqueous solution containing sulfuric acid. The method for producing an optical waveguide according to claim 3, wherein the pH of the acidic aqueous solution is greater than 0 and less than or equal to 5. The method for producing an optical waveguide according to any one of claims 1 to 8, wherein the alkaline developing solution is an alkaline aqueous solution. The method for producing an optical waveguide according to any one of the preceding claims, wherein the alkaline developing solution is an alkaline semi-aqueous developing solution comprising an aqueous alkaline solution and one or more organic solvents. . The method for producing an optical waveguide according to any one of claims 1 to 10, wherein the photosensitive resin layer is formed by applying the photosensitive resin composition. The method for producing an optical waveguide according to any one of the first to tenth aspect, wherein the photosensitive resin layer is formed by laminating a photosensitive resin film composed of the photosensitive resin composition. . The method for producing an optical waveguide according to any one of claims 1 to 12, wherein the photosensitive resin composition is a resin comprising a compound having at least one of a carboxyl group and a phenolic hydroxyl group. Composition. An optical waveguide tube which utilizes items 1 to 13 as claimed in the patent application The method of manufacturing according to any one of the preceding claims. For example, the optical waveguide of the invention of claim 14 has a light propagation loss of 0.3 dB/cm or less. The optical waveguide according to claim 14 or 15, wherein the optical waveguide is subjected to a high-temperature and high-humidity test for a temperature of 85 ° C and a humidity of 85% for 1000 hours. The light propagation loss is less than or equal to 0.3 dB/cm. The optical waveguide according to any one of claims 14 to 16, wherein the optical waveguide is subjected to 1000 temperature cycling tests between the temperature of -55 ° C and 125 ° C. The light propagation loss is less than or equal to 0.3 dB/cm. The optical waveguide according to any one of claims 14 to 17, wherein the optical waveguide has a light propagation loss after performing a reflow test at a maximum temperature of 265 ° C for the optical waveguide. Less than or equal to 0.3 dB/cm.